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EP0170101B1 - Procédé de préparation d'oxydes de phosphanes tertiaires - Google Patents

Procédé de préparation d'oxydes de phosphanes tertiaires Download PDF

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Publication number
EP0170101B1
EP0170101B1 EP85108328A EP85108328A EP0170101B1 EP 0170101 B1 EP0170101 B1 EP 0170101B1 EP 85108328 A EP85108328 A EP 85108328A EP 85108328 A EP85108328 A EP 85108328A EP 0170101 B1 EP0170101 B1 EP 0170101B1
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EP
European Patent Office
Prior art keywords
methylphenyl
sulfide
phosphansulfid
phosphine
bis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP85108328A
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German (de)
English (en)
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EP0170101A1 (fr
Inventor
Erwin Dr. Weiss
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Hoechst AG
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Hoechst AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides

Definitions

  • the invention relates to a process for the preparation of tertiary phosphine oxides by treating tertiary phosphine sulfides with hydrogen peroxide with a solvent.
  • the oxidative conversion of the tertiary phosphine sulfides into the corresponding phosphine oxides can, for. B. SOC1 2 , KMn0 4 or HN0 3 ; see. the article by L. Maier "Organic phosphorus compounds" in Helvetica Chimica Acta 47, pp. 120-132, in particular pp. 124/125 (1964).
  • the following reaction equations are given in this reference for the oxidation with the 3 reagents mentioned:
  • the aromatic nuclei present are also nitrided.
  • the object was therefore to find an improved process for converting tertiary phosphine sulfides into the corresponding phosphine oxides.
  • This object was achieved according to the invention by using - optionally halogenated - aliphatic C 1 -C 6 -carboxylic acids and / or their anhydrides as solvents or at least as solvent components in the oxidation of tertiary phosphine sulfides with H 2 0 2 .
  • the object of the invention is therefore a process for the preparation of tertiary phosphine oxides by an oxidative treatment of tertiary phosphine sulfides with H 2 0 2 in a solvent;
  • the process is characterized in that a solvent is used which contains at least about 20% by weight, preferably at least 50% by weight, optionally halogenated - aliphatic C 1 -C 6 -carboxylic acids and / or their anhydrides and the rest consists of miscible other inert solvents. It is particularly preferred to use only - optionally halogenated - aliphatic C 1 -C 6 -carboxylic acids and / or their anhydrides, in particular only Acetic acid to use.
  • the carboxylic acids and their anhydrides can be used either individually or in a mixture with one another. They should make up at least about 20% by weight, preferably at least about 50% by weight, of the total solvent. It is particularly preferred if these carboxylic acids and / or their anhydrides are the sole solvent.
  • the sole solvent is very particularly preferably acetic acid (glacial acetic acid).
  • the mixture components must be miscible with the carboxylic acids and / or their anhydrides; in addition, of course, they must not undesirably react with the hydrogen peroxide and the starting and end products of the reaction. Possible such mixture components are therefore z.
  • water (C 1 -C 6 ) alcohols such as.
  • methanol or ethanol lower aliphatic halogenated hydrocarbons such.
  • methylene chloride, 1,2-dichloroethane etc. aromatic hydrocarbons such.
  • aromatic chlorinated hydrocarbons such.
  • mixture components water and alcohols are only useful in a mixture with the aforementioned carboxylic acids, not with their anhydrides, because the acids or esters form with the anhydrides. If the acids are intended as solvents, they are advantageously used as such and not generated from the anhydrides and water.
  • R 1 , R 2 and R 3 independently of one another optionally substituted by inert groups C 1 -Ci2-alkyl-C6-Cio-aryl and C 6 -C 2Q aralkyl groups
  • the substituents are preferably halogen atoms, in particular only F and / or CI atoms.
  • Preferred inert substituents for the aryl and aralkyl groups are also alkyl radicals (preferably with up to 4 carbon atoms).
  • Hydrogen peroxide can be used as an approximately 3 to 85% aqueous solution, expediently in the commercially available form (approximately 30 to 35%).
  • the hydrogen peroxide is preferably used in an approximately equimolar amount, based on the starting phosphine sulfide. A slight excess of up to about 5% is advantageous; further surpluses are possible, but are no longer an advantage.
  • the phosphine sulfides are dissolved or suspended in the solvent.
  • the ratio of phosphine sulfide: solvent can vary within wide limits. A weight ratio of approximately 1: (1-20) is advantageous.
  • the solution or suspension becomes. at temperatures of generally between about -5 and +100 ° C, preferably between +40 and +80 ° C, hydrogen peroxide metered in as an aqueous solution. Since the reaction is exothermic, cooling may be required. Accordingly, cold solutions or suspensions of phosphine sulfides do not have to be preheated in order to achieve the desired reaction temperature; on the contrary, it is possible to use the heat of reaction itself to achieve the desired temperature.
  • reaction mixture is worked up in a manner known per se by filtration of the cooled solution from the sulfur which normally occurs in elemental form.
  • the phosphine oxides After the solvent has been distilled off (preferably in vacuo), the phosphine oxides usually remain initially as oily carboxylic acid adducts.
  • the free phosphine oxides can easily be obtained in pure form by heating in vacuo or distillation. It is also possible to stir the carboxylic acid adducts in water and, if necessary, to cleave them by neutralization with bases.
  • the free phosphine oxides precipitate out of the aqueous, optionally alkaline, solution and can be filtered off or - if liquid - separated as a second phase.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)

Claims (5)

1. Procédé pour préparer des oxydes de phosphines tertiaires par un traitement oxydant de sulfures de phosphines tertiaires au moyen de peroxyde d'hydrogène dans un solvant, procédé caractérisé en ce qu'on utilise un solvant qui est constitué, pour au moins environ 20 % en poids, de préférence pour au moins 50 % en poids, d'acides carboxyliques aliphatiques en C1-C6, éventuellement halogénés, et/ou de leurs anhyd.rides, et, pour le reste, d'autres solvants inertes miscibles avec les précédents.
2. Procédé selon la revendication 1 caractérisé en ce que le solvant est constitué exclusivement d'acides carboxyliques aliphatiques en C1-C6, éventuellement halogénés, et/ou d'anhydrides de tels acides, plus particulièrement exclusivement d'acide acétique.
3. Procédé selon l'une des revendications 1 et 2, caractérisé en ce qu'on utilise, comme sulfures de phosphines tertiaires, des composés répondant à la formule :
Figure imgb0010
dans laquelle R1, R2 et R3 représentent chacun, indépendamment les uns des autres, un radical alkyle en C1-C12. aryle en C6-C10 ou aralkyle en C6-C20' éventuellement porteurs de substituants inertes.
4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'on utilise le peroxyde d'hydrogène en une quantité à peu près équimolaire par rapport au sulfure de phosphine de départ.
5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'on effectue le traitement oxydant à des températures comprises entre environ -5 et +100 °C, de préférence entre +40 et +80 °C.
EP85108328A 1984-07-20 1985-07-05 Procédé de préparation d'oxydes de phosphanes tertiaires Expired EP0170101B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843426721 DE3426721A1 (de) 1984-07-20 1984-07-20 Verfahren zur herstellung tertiaerer phosphanoxide
DE3426721 1984-07-20

Publications (2)

Publication Number Publication Date
EP0170101A1 EP0170101A1 (fr) 1986-02-05
EP0170101B1 true EP0170101B1 (fr) 1988-05-25

Family

ID=6241100

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85108328A Expired EP0170101B1 (fr) 1984-07-20 1985-07-05 Procédé de préparation d'oxydes de phosphanes tertiaires

Country Status (5)

Country Link
US (1) US4675446A (fr)
EP (1) EP0170101B1 (fr)
JP (1) JPS6137792A (fr)
CA (1) CA1234839A (fr)
DE (2) DE3426721A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3532360A1 (de) * 1985-09-11 1987-03-19 Hoechst Ag Verfahren zur herstellung tertiaerer phosphanoxide
DE3532359A1 (de) * 1985-09-11 1987-03-19 Hoechst Ag Verfahren zur herstellung bifunktioneller tertiaerer aromatischer phosphanoxide
DE3544065A1 (de) * 1985-12-13 1987-06-19 Roehm Gmbh Verfahren zur herstellung von tertiaeren phosphinoxiden
EP0630877B1 (fr) * 1993-06-21 1997-03-12 Shin-Etsu Chemical Co., Ltd. Procédé de traitement des produits de réaction de type Wittig
DE19532051A1 (de) * 1995-08-31 1997-03-06 Basf Ag Verfahren zur Reinigung tertiärer Phosphinoxide

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3053900A (en) * 1959-07-20 1962-09-11 Monsanto Chemicals Preparation of phosphine sulfides
DE1268619B (de) * 1967-01-13 1968-05-22 Bayer Ag Verfahren zur Herstellung von Addukten von Wasserstoffperoxyd an tertiaere Phosphinoxide, Arsinoxide und Stibinoxide
JPS58121295A (ja) * 1982-01-12 1983-07-19 Shionogi & Co Ltd ホスフインスルフイドをオキシドに変換する方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Römpps Chemie-Lexikon, 8. Auflage, 1985, Seiten 3156-3157 *

Also Published As

Publication number Publication date
JPS6137792A (ja) 1986-02-22
DE3426721A1 (de) 1986-01-23
CA1234839A (fr) 1988-04-05
US4675446A (en) 1987-06-23
EP0170101A1 (fr) 1986-02-05
DE3562919D1 (en) 1988-06-30

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